Theoretical insights into covalency driven f element separations
Through Density Function Theory (DFT) calculations, we set out to understand the structures and stabilities of the aqueous phase complexes [M(III)(DTPA)-H(2)O](2-) (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. All bonding analyses su...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2013-01, Vol.42 (7), p.2636-2642 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Roy, Lindsay E Bridges, Nicholas J Martin, Leigh R |
| description | Through Density Function Theory (DFT) calculations, we set out to understand the structures and stabilities of the aqueous phase complexes [M(III)(DTPA)-H(2)O](2-) (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. All bonding analyses suggest that the preference of the DTPA(5-) ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates providing an additional, yet small, covalent interaction. These results question the exclusive use of hard and soft acids and bases (HSAB) concepts for the design of extracting reagents and suggest that hard-soft interactions may play more of a role in the separations process than previously thought. |
| doi_str_mv | 10.1039/c2dt31485a |
| format | Article |
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All bonding analyses suggest that the preference of the DTPA(5-) ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates providing an additional, yet small, covalent interaction. 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All bonding analyses suggest that the preference of the DTPA(5-) ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates providing an additional, yet small, covalent interaction. These results question the exclusive use of hard and soft acids and bases (HSAB) concepts for the design of extracting reagents and suggest that hard-soft interactions may play more of a role in the separations process than previously thought.</description><subject>Bonding</subject><subject>Complexation</subject><subject>Covalence</subject><subject>Density</subject><subject>Density Functional Theory</subject><subject>Ligands</subject><subject>Mathematical analysis</subject><subject>Neodymium</subject><subject>NUCLEAR FUEL CYCLE AND FUEL MATERIALS</subject><subject>Separation</subject><subject>TALSPEAK</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNqF0UtLAzEUBeAgitbHxh8ggysRqsm9eUx2Sn1CwU1dD2l6x0amkzpJC_57R1vdurpn8XG4cBg7FfxKcLTXHmYZhSyV22EDIY0ZWkC5-5dBH7DDlN45B-AK9tkBIAAqgwN2M5lT7CgH75oitCm8zXPqQ46Fj2vXUOs_i1kX1tQWdUENLajNRaKl61wOsU3HbK92TaKT7T1irw_3k9HTcPzy-Dy6HQ-9VDwPSaDGaQlKo5UzT0Ypp00tp6Ak17UsuVSOSwlaKs2t89zWRtagQDphFeIRO9_0xpRDlXzI5Oc-ti35XAlecjTQo4sNWnbxY0UpV4uQPDWNaymuUiUMcl6KUvP_KQqljbCg_6dg0Fgrsezp5Yb6LqbUUV0tu7Bw3Wf_YvU9VjWCu8nPWLc9Ptv2rqYLmv3R33XwC3V9i6s</recordid><startdate>20130101</startdate><enddate>20130101</enddate><creator>Roy, Lindsay E</creator><creator>Bridges, Nicholas J</creator><creator>Martin, Leigh R</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7U5</scope><scope>8FD</scope><scope>L7M</scope><scope>7SR</scope><scope>8BQ</scope><scope>JG9</scope><scope>OTOTI</scope></search><sort><creationdate>20130101</creationdate><title>Theoretical insights into covalency driven f element separations</title><author>Roy, Lindsay E ; Bridges, Nicholas J ; Martin, Leigh R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c450t-e1363b8256394dce755a67f4b25406f48045a0442645609ac09f74f2524a19533</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Bonding</topic><topic>Complexation</topic><topic>Covalence</topic><topic>Density</topic><topic>Density Functional Theory</topic><topic>Ligands</topic><topic>Mathematical analysis</topic><topic>Neodymium</topic><topic>NUCLEAR FUEL CYCLE AND FUEL MATERIALS</topic><topic>Separation</topic><topic>TALSPEAK</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Roy, Lindsay E</creatorcontrib><creatorcontrib>Bridges, Nicholas J</creatorcontrib><creatorcontrib>Martin, Leigh R</creatorcontrib><creatorcontrib>Idaho National Laboratory (INL)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Materials Research Database</collection><collection>OSTI.GOV</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Roy, Lindsay E</au><au>Bridges, Nicholas J</au><au>Martin, Leigh R</au><aucorp>Idaho National Laboratory (INL)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Theoretical insights into covalency driven f element separations</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2013-01-01</date><risdate>2013</risdate><volume>42</volume><issue>7</issue><spage>2636</spage><epage>2642</epage><pages>2636-2642</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>Through Density Function Theory (DFT) calculations, we set out to understand the structures and stabilities of the aqueous phase complexes [M(III)(DTPA)-H(2)O](2-) (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. 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| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2013-01, Vol.42 (7), p.2636-2642 |
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| language | eng |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Bonding Complexation Covalence Density Density Functional Theory Ligands Mathematical analysis Neodymium NUCLEAR FUEL CYCLE AND FUEL MATERIALS Separation TALSPEAK |
| title | Theoretical insights into covalency driven f element separations |
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